Fungicidal compositions and methods utilizing metal complexes

ABSTRACT

METAL COMPLEXES PREPARED BY REACTING (1) ORGANIC COMPOUNDS HAVING THE FORMULA   2-(R-OOC-NH-)BENZIMIDAZOLE   WHEREIN R IS LOWER ALKYL, AND (2) METAL SALTS, SUCH AS ZINC CHLORIDE OR COPPER ACETATE, ARE USEFUL AS FUNGICIDES.

United States Patent 3,705,939 FUNGICIDAL COMPOSITIONS AND METHODSUTILIZING METAL COMPLEXES Hein L. Klopping, Wilmington, Del., assignorto E. I. du Pont de Nemours and Company, Wilmington, Del.

No Drawing. Continuation-impart of application Ser. No. 777,171, Nov.19, 1968. This application Oct. 21, 1969, Ser. No. 868,233

Int. Cl. 001d 49/38 US. Cl. 424-245 8 Claims ABSTRACT OF THE DISCLOSUREMetal complexes prepared by reacting (1) organic compounds having theformula wherein R is lower alkyl, and (2) metal salts, such as zincchloride or copper acetate, are useful as fungicides.

CROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of my copending application Ser. No. 777,171, filedNov. 19, 1968.

BACKGROUND OF THE INVENTION This invention relates to a group ofcomplexes prepared by reacting (1) 2-benzimidazolecarbamic acid estersand (2) salts; to methods of making said complexes; and to methods ofusing said complexes to control fungi.

The survival of man has been dependent upon his ability to protectplants and their products which satisfy his basic needs from variousagents of destruction such as fungi. With the rapidly increasingpopulation of the world it becomes imperative that there be continuingimprovements in the efliciency of the materials and the methods employedto provide this protection, These improvements can be in the form ofeffective control of more kinds of pests or in the form of requiringless material or work. The materials and methods of this inventionrepresent marked advances in both of these possible areas ofimprovement, as will be explained more fully.

It has been discovered that application of the complexes of thisinvention by the methods of this invention entirely precludes or reducesdamage to plants and inanimate organic materials due to fungi. Fungusmycelia are killed or prevented from developing further by the presenceof one or more of the compounds, i.e., the compounds are fungicidal orfungistatic.

The compounds and methods of this invention also make possible thecontrol of damage by fungi with an amazingly small amount of chemicaland with surpris ingly little effort.

SUMMARY OF THE INVENTION It has been found that outstanding fungicidalactivity can be obtained by applying to the locus of a fungusinfestation, an effective amount of a complex of (1) an organic compoundhaving the formula:

3,705,939 Patented Dec. 12, 1972 wherein R is methyl, ethyl, isopropyl,or sec-butyl, and (2) a salt selected from the group consisting of:

O I 1 copper (II) propionate [Cu(O-OCH:CH; g

The most preferred complex is 2-benzimidazolecarbamic acid, methyl,ester, 2:1 complex with zinc chloride.

It should be understood that benzimidazolecarbamates exist in tautomericforms, i.e.,

III H n o H o DETAILED DESCRIPTION OF THE INVENTION Several complexescan be formed according to the process of the invention. The complexesmay be either 2:1 or 1:1 complexes. A 2:-1 complex is a complex havingtwo molecules of the 2-benzimidazole and 1 molecule of the salt whereasa 1:1 complex contains one molecule of the 2-benzimidazole and onemolecule of the salt.

2:1 Complexes Complexes having two molecules of the2-benzimidazolecarbamate and one molecule of salt can be prepared fromany suitable 2-benzimidazolecarbamate and a salt selected from the groupconsisting of zinc chloride, zinc bromide, copper(II) chloride, andcopper(II) bromide. The zinc 2:1 complexes of this invention have thechemical formula:

R is methyl, ethyl, isopropyl or sec-butyl; and X is chlorine orbromine.

The copper 2:1 complexes have the chemical formula:

wherein R is methyl, ethyl, isopropyl, or sec-butyl; and Y is chlorineor bromine.

While the exact chemical structure and bonding of these 2:1 complexes isnot known with certainty, in the case of the zinc complexes it isbelieved that the salt is probably bonded to theZ-benzimidazolecarbamate by four coordinate bonds. Thus the zinc 2: 1complexes may have the general structural formula:

(I wherein R and X are defined above.

Thus, a 2-benzimidazolecarbamic acid, methyl ester-2:1- complex withzinc chloride is believed to have the formula:

p H v) It should be noted that in the case of these zinc 2:1 complexes,the metal is present in the form of an electrically neutral salt.Likewise, while the exact chemical structure of the copper 2:1 complexesis not known, it is believed that they may be represented by the generalstructural R is methyl, ethyl, isopropyl, or sec-butyl; and Z ischlorine or bromine.

It is theorized that three coordinate and one ionic bond unite thecopper atom and the benzimidazolecarbamic acid group. AZ-benzimidazolecanbamic acid, methyl ester- 2:1-complex with copperfl l)monochloride would have (VII) 1:1 Complexes Complexes having onemolecule of Z-benzimidazole and one molecule of metal salt can beprepared from any suitable 2-benzimidazole and a salt selected from thegroup consisting of zinc acetate, zinc propionate, copperQH) chloride,copper(II) bromide, copperfll) acetate, and copper(-II) propionate. The1:1 complexes have the chemical formula:

(VIII) wherein:

R is methyl, ethyl, isopropyl or sec-butyl;

M is zinc or copper; and

X is acetate or propionate when M is zinc and is chlorine, bromine,acetate, or propionate when M is copper. As in the case of 2:1complexes, the exact structure of the 1:1 complexes is uncertain. The1:1 complexes may have the structure wherein:

p "ou++-oon o-o (X) in this case, the salt is bonded to the2-benzimidazolecarbamate by one ionic and one coordinate bond. Sinceonly one acetate ion is present, the 1:1 complex is namedZ-benzimidazolecarbamic acid, methyl ester, 1:1 complex with copperfll)monoacetate.

Preparation of complexes The complexes of this invention are prepared byreacting a 2-benzimidazolecarbamic acid ester of Formula I with one ofthe eight salts listed above. The reaction may be performed such that aslurry of the 2-benzimidazolecarbamate is reacted with an aqueoussolution of the salt.

In carrying out the reaction, the order of addition is not critical. Insome cases, the Z-benzimidazolecarbamate is hard to wet with aconcentrated solution of the salt. In these cases, it is advantageous tofirst thoroughly wet the Z-benzimidazolecarbamate with water beforemixing same with the salt solution. Also, it is permissible, but notnecessary, to use an organic solvent such as ethyl acetate to wet thebenzimidazolecarbamate. The solvent may be left in the reaction mixtureduring the subsequent reaction.

The concentration of the Z-benzimidazolecarbamate in the aqueous slurryis not critical and can vary from very dilute to about by weight.However, very dilute concentrations are not economical in light of thelarge amount of water which must be used and the large size of equipmentrequired. Concentrations above about 20% are diflicult to stirefficiently. The concentration of the metal salt is not critical,although it is preferred to use concentrated or saturated solutions,e.g., 66% by weight or higher in the case of zinc chloride. Since thesalt solutions often contain large excesses of metal salt, it iseconomically advantageous to recover any filtrates for use in subsequentoperations. While concentrated solutions are preferred, good results canbe obtained by using dilute solutions of the salt. The total quantity ofmetal salt present in the reaction mixture can vary from the theoreticalamount to an excess of well over 1000%.

The particle size of the 2-benzimidazolecarbamate suspended in the metalsalt solution is not critical. Small particle sizes are advantageous inbringing about an increase in rate of reaction; however, at very smallparticle sizes the 2-benzimidazole may be hard to wet with the saltsolution. Accordingly, inert wetting, dispersing, or emulsifying agentscan in some cases be useful in improving the reaction conditions.

The time required to complete the reaction is not critical and can vary,for example, from a few seconds to 16 hours or more. Many factorsinfluence reaction time, such as: temperature, concentration ofreactants, particle size of the 2-benzimidazolecarbamate, etc. In eachcase the optimum conditions can be determined experimentally.Completeness of the reaction is best determined by the appearance anddisappearance of certain peaks in the IR spectrum, as described in theexamples.

The temperature at which the reaction proceeds is significant in somecases in regard to the product formed, whereas in other cases thetemperature effects only the rate of reaction. For example, in reacting2-benzimidazolecarbamic acid esters with copper(II) chloride at atemperature of about 100 C., a 1:1 complex with copper(II) monochlorideis obtained, while at room temperature a 2:1 complex with copper(II)chloride is obtained as shown in Examples 3 and 4. In general, thereaction temperature can vary between around room temperature to about130 C.

The presence of foreign ions, such as those which are produced duringthe production of the 2-benzimidazolecarbamic acid esters from alkylchloroformates, cyanamide, and ortho-phenylene diamine, do not interferewith the coupling formation. Thus, it is not necessary to purify thestarting 2-benzimidazolecarbamate prior to starting the reaction.

The complexes of this invention can be made either batchwise or on acontinuous basis.

The following examples illustrate the preparation of the complexes ofFormula I. The amounts are given in terms of parts by weight unlessotherwise specified.

6 EXAMPLE 1 Preparation of 2-benzimidazolecarbamic acid, methyl ester,2:1 complex with zinc chloride Fifty seven and three tenths (57.3) partsof Z-benzimidazolecarbamic acid, methyl ester is mixed with a solutionof 273 parts of zinc chloride in 2500 parts of water. With vigorousstirring, the mixture is heated to reflux and kept at reflux temperaturefor 30 minutes. Then, the mixture is cooled and filtered, and the filtercake is washed thoroughly with water and dried, giving 696 parts of theproduct.

In the infrared spectrum the peaks at 5.84 and 7.90 1, which arecharacteristic for 2-benzimidazolecarbamic acid, methyl ester, are nolonger present and new peaks at 5.75 and 8.07 which are characteristicfor the zinc chloride complex, have appeared- This product may be usedas such or in formulated form for antifungal application, even though itcontains approximately 10% of starting material.

Analysis.Calculated for a mixture of by weight of 2:1 ester, zincchloride complex (C H N O ZnC1 and 10% by weight of organic startingmaterial (percent): C, 43.15; H, 3.6; N, 16.8; C1, 12.3; Zn, 11.3.

Product of Example 1 found (percent): C, 42.92; H, 3.61; N, 16.58; Cl,12.63; Zn, 11.3.

The above product is purified as follows. 5.0 parts of the material isextracted with 200 parts of boiling acetonitrile and the hot mixturefiltered. The insoluble material (0.5 parts) exhibits an IR spectrumidentical with that of Z-benzimidazolecarbamic acid, methyl ester. Theacetonitrile filtrate is vacuum-concentrated to a small volume, cooled,and the precipitated solid (4 parts after air-drying) is collected on afilter. It consists of purely white, fluffy needles, and its IR spectrumis essentially the same as that of the crude product (characteristicpeaks at 5.75 and 8.07 1). Evaporation of the mother liquor affordsanother 0.5 parts of somewhat impure product.

The air-dried needles analyze for a product containing approximately 2%water, as shown by the following results:

Analysis.--Calculated for 2 benzimidazolecarbamic acid, methyl ester,2:1 complex with zinc chloride containing 2% Water (percent): C, 40.9;H, 3.6-5; N, 15.91; Cl, 13.4; Zn, 12.35. Found (percent): C, 41.19; H,3.40; N, 15.91; Cl, 13.12; Zn, 12.3.

The complex probably has the structure shown in Formula III above.

EXAMPLE 2 Preparation of 2-benzimidazolecarbamic acid, methyl ester, 1:1complex with zinc monoacetate Fifty-seven parts of2-benzimidazolecarbamic acid, methyl ester is mixed with a solution of367 parts of anhydrous zinc acetate in 600 parts of Water. With vigorousstirring, the slurry is heated to reflux and kept at reflux temperaturefor 2 /2 hours. The mixture is then cooled, filtered, the solid washedthoroughly with water, and air-dried. The product consists of 70 partsof a white powder. The IR spectrum showed characteristic peaks atapproximately 5.7 and 8.1 Peaks at 5.84 and 7.90;, which arecharacteristic for the organic starting material, were absent.

Analysis.-Calculated for 2 benzimidazolecarbamic acid, methyl ester, 1:1complex with zinc monoacetate (C H N Q Zn) containing 1.5% H 0(percent): C, 41.4; H, 3.6; N, 13.55; Zn, 20.5. Found (percent): C,41.34; H, 3.94; N, 13.56; Zn, 19.26.

This complex probably has the following structure:

Preparation of Z-benzimidazolecarbamie acid, methyl ester, 1:1 complexwith copper(II) monochloride To a solution of 340 parts of copper(II)chloride dihydrate in 250 parts of water is aded 57 parts of finelyground 2-benzimidazolecarbamic acid, methyl ester. The mixture isstirred and heated on a steambath for 4 hours. The very dark reactionmixture is cooled and diluted with water, whereby the color changes togreen. The mixture is filtered, and the solid is washed thoroughly withWater and air-dried to 57 parts of the product, a green powder.

Analysis.-Calcd. for C H N CuCl (percent): C, 37.3; H, 3.1; N, 14.5.Found (percent): 'C, 37.09; H, 3.68; N, 14.53. The infrared spectrumshows characteristic peaks at 5.75 and 8.04

This complex probably has the formula:

C (XII) EXAMPLE 4 Preparation of 2-benzimidazolecarbamic acid, methylester, 2:1 complex with copper(II) monochloride To a solution of 340parts copper(II) chloride dihydrate in 400 parts of water is added 57parts of finely divided 2-benzimidazolecarbamic acid, methyl ester. Themixture is stirred at room temperature for 16 hours. It is thenfiltered, the solid Washed with water (whereby the color turns fromgreen to brown), then with acetone, and air-dried. The infrared spectrumshows a peak at 5.85 1 which is much stronger than that of the startingmaterial, and a characteristic peak at 8.05 ,u..

Analysis.-Calc. for 2 -benzimidazolecarbamic acid, methyl ester 2:1complex with copper(II) monochloride (C H N O CuCl) containing 1 /2% HO: C, 44.3; H, 3.9; N, 17.2. Found: C, 44.29; H, 3.98; N, 17.37.

EXAMPLE Preparation of Z-benzimidazolecarbamic acid, isopropyl ester,2:1 complex with zinc chloride Thirty-one parts ofZ-benzimidazolecarbamic acid, isopropyl ester is stirred with 200 partsof water until the solid is thoroughly Wetted and suspended in thewater. Then, a solution of 191 parts of zinc chloride in 380 parts ofwater is added, and the mixture is heated to reflux combined withstirring. After boiling under reflux for two hours, the mixture iscooled and filtered and the solid is washed with Water and dried, giving37 parts of the product as a white solid. The IR spectrum showscharacteristic peaks at 5.75 and 8.05 and very Weak peaks at 5.9 and 7.9indicating the presence of some organic starting material.

In contrast with Example 1, the product in this case is insoluble inacrylonitrile (and acetone) whereas the starting material (the isopropylester) is soluble in acetonitrile and particularly in acetone.Therefore, in order to remove the organic starting material, the crudeproduct is stirred in 300 parts of acetone, filtered, washed with 300parts of acetone, and dried. The infrared spectrum no longer shows theweak peaks at 5.9 and 7.911. but the strong peaks at 5.75 and 8.05p. arestill present.

EXAMPLE 6 Preparation of Z-benzimidazolecarbamic acid, methyl ester 2:1complex with zinc chloride, starting from a crude aqueous slurry of2-benzimidazolecarbamic acid, methyl ester Methyl chloroformate (79.5parts) and 50% sodium hydroxide (131 parts) are added simultaneouslywith good agitation to a solution of cyanamide (34.6 parts) in 165 partsof water. The separate addition rates are controlled so that the pHremains between 6.5 and 7.5. The temperature is kept at 50 C. or belowby external cooling.

To this reaction mass are added o-phenylenediamine (75.3 parts) andenough concentrated hydrochloric acid to give a pH of 4.0. The mixtureis then heated and stirred for an hour at C. while the pH is maintainedat 4.0 by the intermittent addition of concentrated hydrochloric acid.The resulting slurry contains 123.0 parts of Z-benzi'midazolecarbamicacid, methyl ester.

Zinc chloride (275 parts) is added to the hot slurry. The mixture isstirred at 95 C. for another 20 minutes, cooled to 50 C. and filtered.The product is Washed with water and dried in a 'vacuum oven at C. Theinfrared spectrum of this product is identical with that of Example 1.

EXAMPLES 7-17 Using the indicated starting materials and the method ofthe example indicated, several complexes of this invention are prepared.

Procednre of Example example Starting materials Resulting complex2-henzim' idazole- (a) Z-benzxmdazoleearbamic aeid, carbamm 301d 7 1methyl methyl t (b) Zine bromide".-- grgg gf d (a) 2-benzimidazole- 8 2carbamic acid, $3 2 y ester, 1.1

gs g complex with zinc X c prop 2 Ignonoprapiorllate. (a)2henzimidazole- 911mm. 9 1 earbamie acid, ggfi ig g i ethyl ester coniplex t i ith zinc (is) Zinc chloride ghloridea 1 2 enzimi azo egi'gggfig earbamic acid, 10 a ethyl ester. ff ester: 1:1

omplex with copg zgg per(II) monoe or chloride. (a) flrbenzimidazole-2benzim.idaxelecarbamic acid, carbamic acid, 11 4 isopropyl ester.isopropyl ester, 2:1

(b)h(llop per(ll) gigiplex copper e on e. monoc on e. (a)Z-benzimidgzole- 2-bengimidalolgcarbamie aci ear amic sci 12 2 1isopropyl ester. isopropyl ester, 1:1

(b) Copgerfll) complex with copper ehlori e. 2 11) EInQggfihiOlidB. (a)Z-benzimidalole- .3 meme arrests see-butyl ester. com i 1 g (b) Zinechloride"..- g c (a) Z-benzimidazole 2-benzimidazoleearbamie acid,earbamie acid 14 4 methyl ester. methyl ester, 2:1

(bl)3 Copgerfll) Ei%iI)1%l-EX wiith copper IOml 9. ronn 6. (a)2-benzimidazole- Z-benzimidazoleearbamic acid, earbarnic acid, 15 2methyl ester. methyl ester, 121

[(b) Copperfll) complex with copper prepionate. (II) monopropionate.

Procedure of Example example Starting materials Resulting complex (a)2-benzimidazole- Z-benzimidazolecarbamic acid, carbamic acid, 16 3methyl ester. methyl ester, 1:1

(b) Oopper(l1) complex with copper bromide. (II) monobromide. (a)2-benzimidazole- Z-benzimidazlecarbamic acid, carbamic acid, 17 2 methylester. methylester, 1:1

(b) Copperfll) complex with copper acetate. (II) monoacetate.

Utility of the complexes The present complexes are useful forcontrolling the effects of fungi.

There are many fungi against which the complexes are active. These maybe represented by, but are not limited to, the following: Venturiainaequalis, which causes apple scab; Podosphaera leucotricha, whichcauses powdery mildew on apple, Uromyces phaseoli, which causes beanrust; Cercospom apii, which causes early blight of celery; Septorz'aapii-graveolentis, which causes late blight of celery; Sclerotiniasclerotiorum which causes white mold on beans and other crops;Cercospora musa'e, which causes Sigatoka disease of banana; Moniliniafructicola and M. laxa, which cause brown rot of stone fruits; Erysiphecichoracearum, which causes powdery mildew on cantaloupe and othercucurbit crops; Penicillium digitatum, which causes green mold oncitrus; Sphaerotheca humuli, which causes powdery mildew on roses;Diplocarpon rosae, which causes black spot on roses; Unicinula necator,which causes powdery mildew on grapes; Coccomyces hiemalis, which causescherry leaf spot; Cladosporium carpophilum, which causes peach scab;Pithomyces chartorum, which grows on turf and pasture grasses andindirectly causes a malady in sheep; Erysiphe graminis hordei, whichcauses powdery mildew on barley; Piricularia or'yzae, which causes riceblast; Puccinia rubigo-vera tritici, P. Coronata and P. glumarum, whichcause leaf rusts of wheat, oats and grasses respectively; Pucciniagramim's tritici, which causes stem rust of wheat; Aspergillus niger,which causes cotton boll rot as well as decay following wounding in manyplant tissues; Aspergillus terreus, which is common in soil and attacksvegetable matter; various species of Rhizoctonia, Fusarium andVerticillium present in soil and attacking the roots or otherunderground parts of a variety of plants; various species of Penicilliumgrowing on such things as fabric, fiber board, leather goods and paint;species of Myrotheciurn attacking such items as shower curtains,carpets, mats and clothing.

The complexes of this invention when applied by the methods of thisinvention enter and move freely within plants, i.e., they are systemic.Thus, fungi can be controlled in plant parts well removed from the pointof application. In view of such movement, the complexes can be appliedbeneficially to certain seeds. For example, the treatment of cucumberseeds with a few grams per 50 kilograms of seed of a compound of thisinvention provides control of powdery mildew (Erysz'phe cichoracearum)on the resulting plants for periods in excess of 40 days. Applicationsto soil also provide control of certain foliage diseases on plantsgrowing in the treated soil. Spray or dust treatments of plant foliageimpart protection against fungi to other foliage on the plant notactually sprayed and to new foliage developing later.

There are important practical advantages associated with the use of aneffective systemic fungicide. Successful application to seed asdescribed above, results in great savings in chemical and applicationcosts. Soil applications which effectively protect entire plants for anextended period also represent similar savings. Distribution within theplant following foliage treatment eliminates the need for frequentretreatment to protect rapidly growing tissue. Also, materials withinthe plant are not subject to removal by rainfall. Similarly, movement ortranslocation of the chemical within the plant can provide protection tothose 10 parts of the plant that may not have been covered by theoriginal spray application. This is of particular importance with plantsof dense growth character resisting the intrusion of the spray and alsoto tall plants, such as shade trees, where the spray will not reach tothe top.

An additional valuable characteristic of the complexes of this inventionis their ability to prevent the spread or to kill fungus infectionalready established within a plant, i.e., they are curative. Thus, thecomplexes need not be applied until after conditions develop whichpermit the actual initiation of fungus attack. This means that, undersome circumstances, it is possible to avoid applying any chemical duringthe entire life of the crop. In other cases, only a part of the normalfull schedule of pesticide application is required. Therefore, greatsavings both in chemical cost and application labor are possible withcompounds capable of systemic and curative performance.

The complexes of this invention provide protection from damage caused byfungi, when applied to the proper locus by the methods describedhereinafter and at a sufiicient rate to exert the desired fungicidaleffect. They are especially suited for the protection of living plantssuch as fruit-bearing trees, nut-bearing trees, ornamental trees, foresttrees, vegetable crops, horticultural crops (including ornamentals,Small fruits and berries), fiber crops,

grain and seed crops, sugarcane, sugar beets, pineapple, forage and haycrops, beans, peas, soybeans, peanuts, potatoes, sweet potatoes,tobacco, hops, turf and pasture.

=Living plants may be protected from fungi by applying one or more ofthe complexes of this invention to the soil in which they are growing orin which they may subsequently be seeded or planted; or to seeds,tubers, bulbs or other plant reproductive parts prior to planting; aswell as to foliage, stems and fruit of the living plant. Living plantscan also be protected by dipping the root system or physically injectingthe chemical or chemicals into roots or stenrs.

Soil applications are made with dusts, granules, pellets, slurries orsolutions. Preferred rates for application of the compounds of thisinvention to soil in which plants are or will be growing range from 1 to200 parts per million by weight of the soil in which the roots are orwill be growing. More preferred use rates are in the range of 2 to 50parts per million.

Preferred rates for application to seeds, tubers, bulbs or other plantreproductive parts, range from 50 to 2000 grams of active compound ofthis invention per 50 kilograms of planting material treated. Morepreferred rates are in the range of to 1000 grams of active compound per50 kilograms. Applications are made from dusts, slurries or solutions.Such treatments protect the treated parts themselves from damage due tofungi and in ailldition, impart extended protection to the resulting newp ants.

Preferred rates for application of the compounds of this invention tofoliage, stems and fruit of living plants range from 20 to 4000 grams ofactive ingredient per hectare. More preferred rates are in the range of40 to 2000 grams per hectare. The optimum amount within this rangedepends upon a number of variables which are well-known to those skilledin the art of plant protection. These variables include, but are notlimited to, the disease to be controlled, weather conditions expected,the type of crop, stage of development of the crop, and the intervalbetween applications. Applications within the range given may need to berepeated one or many more times at intervals of 1 to 60 days.

Preferred rates for dip applications to roots of living plants are inthe range of 20 to 1000 grams of active ingredient per 100 liters ofwater or other liquid carrier. More preferred rates are in the range of40 to 500 grams per 100 liters.

Preferred rates for injection into the roots or stems of living plantsare in the range of 1 to 1000 parts per million of water or other liquidcarrier.

Plant parts such as fruits, tubers, bulbs, roots and the like, harvestedfor food or feed, are protected from decay and other deteriorationcaused by fungi during processing, distribution and storage by treatmentwith an active complex of this invention. The plant parts to be soprotected can be dipped in a liquid bath containing the activeingredient, dusted with a finely divided preparation of the activeingredient, sprayed, misted with an aerosol containing the complex orenclosed in wrapping or packing materials impregnated with the activecomplex.

If a liquid bath is used, it can contain an amount of the activeingredient in the range of l to 5000 parts per million of the weight ofthe liquid.

Dusts as well as wrapping or packing materials used for this type ofapplication can contain 0.1 to of the active ingredient.

Wood, leather, fabric, fiber board, paper and other industrial materialsof an organic nature can be protected from decomposition ordiscoloration by fungi by coating, incorporating and impregnating withan effective amount of one or more of the complexes of this invention.The coating can be accomplished by dipping, spraying, flooding, misting(as with an aerosol) or dusting the material to be proteted with asuitable composition containing the active ingredient.

Where incorporation or impregnation procedures are to be employed, userates may be expressed in terms of the amount of active ingredientintroduced into the material to be protected. The preferred use ratesfor these types of applications are in the range of 0.001 to 0.1 percentby weight of active ingredient in the final product.

Surface treatment is by dips, washes, sprays, aerosols or dustapplications. Sprays, dips and washes contain the active complexes ofthe invention at rates of 10 to 5000 parts per million. Fluids foraerosol application and dusts contain 0.1 to by weight.

Painted surfaces can be protected from unsightly stain and mold growthby incorporating in the paint formulation, prior to application, 5 to2,000 parts per million of an active complex of this invention. Suchtreatments with the complex of this invention also protect the paintwhile still in the can from deterioration by fungi.

As was previously set forth, the complexes of this invention areespecially suited for use on living plants. Application to the foliage,stems and fruit of plants at the rate indicated above is generallyaccomplished by employing sprays, dusts, or aerosols containing theproper amount of active ingredient. For the control of fungi which areregularly present, applications often start prior to the time that theproblem actually appears and continue on a pre-determined schedule. Sucha precedure is termed preventive or protective.

With the complexes of this invention, successful control of plantdiseases can also be accomplished by applications made after they arepresent. Fungus mycelia within the plant tissue are actually killed.This approach or effect is termed curative or eradican and permits theuser to realize considerable savings.

Curative control of plant diseases with the complexes of this inventionis enhanced if the treated plant parts are moist for one or more periodsof 2 to 12 hours each soon after the active compound is applied. Oftenthe slow drying of an original spray treatment or naturally occurringrains, mists, fogs or dews will accomplish this. Under othercircumstances, such as during dry periods or in shelters such asgreenhouses, it is necessary to keep the plants moist by some specialelfort for best results.

Curative disease control with the complexes of this invention isimproved by including a proper quantity of a selected surface activeagent in the spray or dust applied to the plant. The most preferredsurface active agents for this purpose include: modified phthalicglycerol alkyd resins, glycol esters, ethoxylated fatty acids, alcoholsulfates, lecithin and lecithin derivatives, isethionates, certainphosphate derivatives and taurates. Somewhat'less preferred but,nevertheless, effective surface active agents include: sulfosuccinatederivatives, ethoxylated fatty esters and oils, ethoxylated alcohols,and dodecyl and tridecyl benzene sulfonates and free acids. Examples ofspecific surface active agents in each of these several categories arelisted in Detergents and Emulsifiers.1967 Annual published by John W.McCutcheon, Inc.

The preferred rates for these surfactants when used in sprays is in therange from 10 to 1000 parts per million of the spray fluid.

For dusts, the preferred surfactants rates are in the range of 1000 to100,000 parts per million of the material actually applied.

As previously mentioned, the complexes of the invention are systemic,thus applications to plants can be accomplished by spraying or dustingabove-ground parts, such as foliage, stems and fruits. For suchapplications, the presence of a surface-active agent in the spray ordust enhances activity. Use rates for the surface active agent here arethe same as for sprays and dusts for preventive or curative control asdiscussed above. Systemic effect from the treatment of above-groundparts is also enhanced by moisture on the treated surfaces for one ormore periods of 2 to 12 hours each.

Systemic control of fungi on plants is also accomplished by applicationsto seeds, tubers, bulbs, or other reproductive parts prior to plantingas well as by application of the chemical to the soil in which theplants to be protected are, or will be, growing. Applications toreproductive parts prior to planting is effected through the use ofsprays, dips, dusts or aerosols containing one or more of the compoundsof this invention. Treatment of soil is accomplished by physical mixingprior to planting, distribution in the furrow at planting time, application in transplant water, placement in the soil in a band or sheetwith specialized equipment, injection through irrigation water or bydistribution on the field surface.

Compositions Compositions can be formed by mixing a complex of thisinvention with an adjuvant. The complexes of this invention can often beused to advantage in combinations or mixtures with one or more of thefungicides, bactericides, insecticides, acaricides, or nematocidesavailable on the market today. The combinations or mixtures can be madeby the applicator just prior to use (as in the tank of a sprayer) orincluded in a single composition by the manufacturer or a subsequentprocessor. Illustrative of the materials that may be included in suchcombinations or mixtures are the following:

1,2,3,4,10,lO-hexachloro-l,4,4a,5,8,8a-hexahydro-1,4-

endoexo-5,8-dimethanonaphthalene (Aldrin);

1,2,3,4,5,6-hexachlorocyclohexane (Lindane);

1,2,4,5,6,7 8,8-octachloro-2,3,3a,4,7,7a-hexahydro-4,7-

methanoindene (Chlordane);

1, 1, l-trichloro-2,2-bis(p-chlorophenyl) ethane (DDT)1,2,3,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-1,4-endoexo-5,8-dimethanonaphthalene(Dieldrin);

1,2,3,4,10,l0-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-1,4-endoendo5,6-dimethanonaphthalene(Endrin);

1,(or 3a) ,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene;

1,1,l-trichloro-2,2-bis(p-methoxyphenyl)ethane methoxychlor)1,1-dichloro-2,2-bis(p-chlorophenyl) ethane (TDE) chlorinated camphenehaving a chlorine content of 67- 69% (toxaphene);

chlorinated terpenes having a chlorine content of ca. 66%

(Strobane) 2-nitro-l,1-bis (p-chlorophenyl)butane;

l-naphthyl N-methylcarbamate (carbaryl);

methylcarbamic acid, ester with 4-(dimethylamino)-3,5-

dimethylphenol;

methylcarbamic acid, ester with 1,3-dithio1an-2-one oxime;

methyl N-methylthiolcarbamate;

methyl methylthiolcarbamate;

0,0-diethyl-O- [2-isopropyl-4-methylpyrimid-6-yl] thiophosphate(diazinon);

0,0-dimethyl-l-hydroxy-2,2,2-trichloroethyl phosphonate;

0,0-dimethyl-S-(1,2-dicarbethoxyethyl) dithiophosphate (Malathion);

0,0-dimethyl-O-p-nitrophenyl thiophosphate (methyl parathion);

0,0-diethyl-O-p-nitrophenyl thiophosphate (parathion);

0,0dimethyl-O-(3-chloro-O-nitrophenyl) thiophosphate;

di-2-cyclopentenyl-4-hydroxy-3-methyl-2-cyclopentenl-one chrysanthemate;

0,0-dimethyl-0,0-(2,2-dichlorovinyl) phosphate mixture containing 53.3Bulan, 26.7% Prolan and 20.0% related compounds;

0,0-dimethyl-O-(2,4,5-trichlorophenyl) phosphorothioate;

0,0-dimethyl-S- (4-oxo-1,2,3,-benzotriazine3 (4H)- yl-methyl)phosphorodithioate (Guthion);

bis-(dimethylamino) phosphonous anhydride;

0,0-diethyl-O-(2-keto-4-methyl-7-a-pyranyl) thiophosphate;

0,0-diethyl (S-ethyl mercaptomethyl) dithiophosphate (phorate);

calcium arsenate;

sodium aluminofluoride;

dibasic lead arsenate;

2'-chloroethyl-1-methyl-2-(p-tert-butylphenoxy) ethyl sulfite;

azobenzene;

ethyl 2-hydroxy-2,2-bis(4-chlorophenyl) acetate;

0,0-diethyl-O-(2-(ethylmercapto) ethyl) thiophosphate;

2,4-dinitro-6-sec-butyl phenol;

O-ethyl O-p-nitrophenylbenzenethiophosphonate (EPN);

4-chlorophenyl-4-chlorobenzene sulfonate;

p-chlorophenyl phenyl sulfone;

tetraethyl pyrophosphate;

1,l-bis-(p-chlorophenyl)ethanol;

1,1-bis-(chlorophenyl)-2,2,2-trichloroethanol;

p-chlorophenyl p-chlorobenzyl sulfide;

bis-(p-chlorophenoxy)methane;

3-( l-methyl-Z-pyrrolidyl) pyridine;

mixed esters of pyrethrolone and cinerolone keto-alcohols and twochrysanthemum acids;

cube and derris, both whole root and powdered;

ryanodine;

mixture of alkaloids known as veratrine;

dl-2-allyl-4-hydroxy-3-methyl-2-cyclopentene-l-one esterified with amixture of cis and trans dl-chrysanthemum monocarboxylic acids;

butoxypolypropylene glycol;

p-dichlorobenzene;

2-butoxy-2-thiocyanodiethyl ether;

naphthalene;

1,1-dichloro-2,2-bis (p-ethylphenyl ethane;

p-dimethylaminobenzenediazo sodium sulfonate;

quinone oxyaminobenzooxohydrazone;

tetramethyl thiuram monosulfide;

tetrarnethyl thiuram disulfide (thiram);

metal salts of ethylene bidithiocarbamic acid, e,g.,

manganese, zinc, iron and sodium salts;

pentachloronitrobenzene;

2,3-dihydro--carboxyanilido-6-methyl-1,4-oxathiin;

n-dodecylguanidine acetatae (dodine);

N-trichloromethylthiotetrahydrophthalimide (captan);

phenylmercury acetate;

14 2,4-dichloro-6-(o-chloroanilino)-s-triazine (Dyrene) N-methylmercuryp-toluenesulfonanilide; chlorophenolmercury hydroxides;nitrophenolmercury hydroxides; ethylmercury acetate; ethylmercury2,3-dihydroxypropyl mercaptide; methylmercury acetate; methylmercury2,3-dihydroxypropyl mercaptide (CeresanL) 3,3 '-ethylenebis(tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazine-Z-thione) (Cylan);

methylmercury dicyandiamide;

N-ethylmercury p-toluenesulfonanilide;

1,4-dichl0ro-2,5-dimethoxy benzene (chloroneb);

metal (e.g., iron, sodium and zinc), ammonium and amine salts ofdialkyldithiocarbamic acids;

tetrachloronitroanisole;

hexachlorobenzene;

hexachlorophene;

methylmercury nitrile;

tetrachloroquinone;

N-trichloromethylthiophthalimide;

5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole;

1,Z-dibromo-3-chloropropene;

dichloropropane-dichloropropene mixture;

ethylene dibromide;

1-chloro-2-nitropropane;

chloropicrin;

sodium dimethyldithiocarbamate;

tetrachloroisophthalonitrile;

2-carboxyamino-l-benzimidazolecarboxylic acid,

dimethyl ester;

streptomycin;

2-( 2,4,5 -trichlorophenoxy) propionic acid;

p-chlorophenoxyacetic acid;

l-naphthaleneacetamide;

N-l-naphthylacetamide;

S-methyl-N-[ (methylcarbamoyl) oxy-thiolacetimidate;

and

S-methyl-N[ (carbamoyl) -oxy] thiolacetimidate.

sulfur fixed coppers Bordeaux mixture The additional pesticides areemployed in mixtures or combinations in amounts ranging from one-tenthto ten times that of the compound or compounds of this invention. Theproper choice of amounts for the added pesticides is readily made by oneskilled in the art of protecting plants from pest depredations.

The use of pesticides such as those listed above in combination with acompound of this invention sometimes appears to greatly enhance theacivity of the compound of the invention. In other words, an unexpecteddegree of activity is sometimes seen when another pesticide is usedalong with a compound of this invention.

Specific illustrations of useful combinations and mixtures, along withrepresentative but not restrictive) applications, follow:

(a) 2-benzimidazolecarbamic acid, methyl ester 2:1 complex with zincchloride and carbaryl in ratios ranging from 1:5 to 1:1 for use on snapbeans to control white mold (Sclerotinia sclerotz'orum) along withinsects such as the Mexicon bean beetle and flea beetles. Where aphidsare a factor, parathion or Diazinon may also be added to the mixture atrates ranging from one-tenth to one-half the level of the carbaryl. The2-benzimidazolecarbamic acid, methyl ester 2:1 complex with zincchloride in the mixture can be replaced by other compounds of thisinvention.

(b) Z-benzimidazolecarbamic acid, isopropyl ester, 2:1 complex with zincbromide and DDT in ratios ranging from 1:6 to 1:1 for use on apple treesto control diseases such as scab and powdery mildew, as well as avariety of insects including the codling moth, the fall Webworm,

and the apple red bug. The Z-benzimidazolecarbamic acid, isopropylester, 2:1 complex with zinc bromide may be replaced in the combinationby other compounds of this invention. The DDT may be replaced bymethoxychlor or Guthion. TDE can be added at the same rate as the otherinsecticide where the red-banded leaf roller is a particular problem.Thiram can be added to the mixture at the same rate as the compound ofthis invention to improve control of certain of the late-season fruitspot diseases.

(c) 2-benzirnidazolecarbamic acid, methyl ester, 1:1 complex withcopper(II) monochloride and Kelthane dicofol in ratios ranging from 1:5to 1:1 for use on squash to control powdery mildew along with red spidermites. The Z-benzimidazolecarbamic acid, methyl ester, 1:1 complex withcopper(II) monochloride may be replaced in this combination by any othercompound of this invention.

(d) 2-benzimidazolecarbamic acid, ethyl ester, 1:1 complex with zincmonopropionate and maneb in ratios of 1:6 to 1:1 for use on tomatoes tocontrol a disease complex involving late blight, early blight(Alternaria), anthracnose (Colletotrichum), and gray leaf spot(Stemphylium). Lannate methomyl may be added to the mixture ininsecticidal amounts to provide control of tomato fruitworm andhornworm. The Z-benZimidazolecarbamic acid, ethyl ester, 1:1 complexwith zinc monopropionate may be replaced in the mixture by any othercompound of the invention.

(e) 2-benzimidazolecarbamic acid, methyl ester, 1:1 complex withcopper-(ID-monoacetate and EPN in ratios ranging from 1:6 to 1:1 for useon grape vines in the field to control powdery mildew, and the grapeberry moth. The 2-benzimidazolecarbamic acid, methyl ester, 1:1 complexwith copper(II) monoacetate may be replaced in such a combination by anyother compound of this invention. Captan and folpet may be added to thecombination at rates ranging from one-half to four times that of thecompound of this invention to provide improved control of dead arm.

(f) 2-benzimidazolecarbamic acid, sec-butyl ester, 1:1 complex with zincmonoacetate along with dodine and wettable sulfur in ratios ranging from1:328 to 121:6 for the superlative control of scab, powdery mildew,black rot, cedar apple rust, and frog-eye leaf spot. Other compounds ofthis invention may be substituted for 2-benzimidazolecarbamic acid,sec-butyl ester, 1:1 complex with zinc monoacetate in such combinations.

(g) Z-benzimidazolecarbamic acid, sec-butyl ester, 2:1 complex with zincchloride and toxaphene in ratios rangmg from 1:3 to 3:1 for use on limabeans to control powdery mildew and anthracnose, as well as insects suchas cutworms, lygus bugs, and caterpillars. Copper sulfate orstreptomycin sulfate may be added to the combination at active levelswhere bacterial diseases are a factor. Other compounds of this inventionmay be substituted for 2- benzimidazolecarbamic acid, sec butyl ester,2:1 complex with zinc chloride in such combinations.

Compositions of this invention can be formulated by mixing a complex ofthis invention with other adjuvants such as one or more surface activeagents.

The surface active agents used in this invention can be wetting,dispersing or emulsifying agent. They may act as Wetting agents forwettable powders and dusts or as dispersing agents for wettable powdersand granules. Surfactants may also enhance the biological activity ofthe 2benzimidazolecarbamic acid ester metal complexes of this invention.Such surface active agents can include such anionic, cationic andnonionic agents as have heretofore been generally employed in plantdisease control compositions of similar type. Suitable surface activeagents are set out for example, in Detergents and EmulsifiersAnuntil-1967 by John W. McCutcheon, Inc. Other surface active agents notlisted by McCutcheon but still eifective dispersants by virtue ofprotective colloid action include methyl cellulose, polyvinyl alcohol,hydroxyethylcellulose, and alkyl substituted polyvinyl pyrrolidones.

Suitable surface active agents for use in compositions of this inventioninclude polyethylene glycol esters with fatty and rosin acids,polyethylene glycol esters with alkyl phenols or with long-chainaliphatic alcohols, polyethylene glycol ethers with sorbitan fatty acidesters, and polyoxyethylenethio ethers. Other suitable surfactantsinclude alkali and alkaline earth salts of alkyl aryl sulfonic acids,alkali and alkaline earth fatty alcohol sulfates, dialkyl esters ofalkali metal sulfosuccinates, fatty acid esters of alkali and alkalineearth isethionates and taurates, alkali and alkaline earth salts oflignin sulfonic acids, methylated or hydroxyethylated cellulose,polyvinyl alcohols, alkyl substituted polyvinyl pyrrolidone, alkali andalkaline earth salts of polymerized alkylnaphthalene sulfonic acids, andlong-chain quaternary ammonium compounds. Anionic and nonionic surfaceactive agents are preferred.

Among preferred wetting agents are sodium alkyl naphthalene sulfonates,sodium dioctylsulfosuccinate, sodium dodecylbenzene sulfonate, ethyleneoxide condensates with alkylated phenols such as octyl, nonyl anddodecyl phenol, sodium lauryl sulfate, and trimethylnonyl polyethyleneglycols. Among preferred dispersing agents are sodium, calcium andmagnesium lignin sulfonates, lowviscosity methyl cellulose,low-viscosity polyvinyl alcohol, alkylated polyvinyl pyrrolidone,polymerized alkyl naphthalene sulfonates, sodium N-oleyl or N-laurylisethionates, sodium N-methyl-N-palmitoyl taurate and dodecylphenolpolyethylene glycol esters.

Compositions of this invention will contain, in addition to surfaceactive agents, solid diluents to produce wettahle powders, dusts, orgranules as desired.

(A) Wettable powders Wettable powders are compositions which usuallycontain inert solid diluents in addition to surfactants. These inertdiluents may serve several purposes. They can act as grinding aids toprevent mill smear and screen binding, they can aid rapid dispersion ofthe mix when placed in water, they can adsorb liquid or low meltingsolid active material to produce a free flowing solid product, they canprevent agglomeration into lumps upon prolonged hot storage and they canpermit preparation of compositions with a controlled amount of activeingredient so that proper dosage is easily measured by the consumer.

Suitable diluents may be either inorganic or organic in origin. Theseinclude the natural clays, diatomaceous earth, synthetic mineral fillersderived from silica or silicates, insoluble salts produced byprecipitation in fluify form such as tricalcium phosphate or calciumcarbonate, and powdered organic diluents such as shell flours, woodflours, corn cob flour or sucrose. Preferred fillers for thecompositions of this invention include kaolin clays, attapulgite clay,nous-Welling calcium magnesium montmorillonites, synthetic silicas,synthetic calcium and magnesium silicates, diatomaceous silica, cobflour, and sucrose.

Wettable powders will normally contain both a wetter and a dispersant.More preferred for dry wettable powders are those anionic and nonionicsurfactants which exist in solid form. Occasionally, a liquid, nonionicsurfactant, normally considered an emulsifying agent can be used toproduce both wetting and dispersion.

Wetting and dispersing agents in wettable powders of this invention,when taken together, will comprise from about 0.5 weight percent to 5.0weight percent of the total composition. The active component will bepresent at a concentration of from about 25% to and diluent makes up thebalance to Where needed a corrosion inhibitor or foaming inhibitor maybe added at rates of 0.1% to 1.0% with a corresponding reduction indiluent.

Dust compositions are those intended for application in dry form withsuitable dusting equipment. Since wind drift is undesirable whenapplying dusts, the most suitable dust diluents are those which aredense and rapid settling. These include kaolinites, talcs,pyrophyllites, ground phosphate rock, Sericite, and ground tobaccostems. However, dusts are usually most easily prepared by diluting anexisting high-strength wettable powder with a dense diluent so that thefinal dust will frequently contain a fraction of light, absorptivediluent as well as the more desirable dense filler.

A wetting agent is desirable in dust formulations so that adhesion todew-covered foliage is enhanced. Dusts made from wettable powders willusually contain sufiicient wetter, but dusts made directly fromunformulated active can contain an added wetting agent. Dry solidanionic or nonionic wetters are preferred.

Dust formulations will normally contain from 5.0 weight percent to 25weight percent of active material, from to 1.0% wetting agent, from 3%to 20% light grinding aid diluent and the balance dense, rapid settlingdiluent. If made by diluting a prepared wettable powder it will alsocontain a small amount of dispersing agent which has no active role whenthe composition is used as a dry dust.

(C) Granules Soil treatments with fungicides can frequently be mostreadily applied with granules. Granular products with the complexes ofthis invention, can be made in a number of ways. The active materialscan be dissolved in a volatile carrier and sprayed upon preformedgranules. They may be mixed as powders with suitable diluents andbinders, then moistened and granulated followed by drying. Powders mayalso be applied to preformed granules by tumbling together and applyinga binder, for example a nonvolatile liquid such as oil, glycol or aliquid nonionic surfactant. Rates of granule disintegration anddispersion of active material in moist soil can be controlled by choiceof added surfactants or selection of the binders used to form thegranule.

Suitable preformed granules include those made from attapulgite clay,granular expanded vermiculite, ground corn cobs, ground nut shells orpreformed kaolinite granules. When active fungicide is placed upon suchcarriers the concentration may range from 1% to 25%. However, it isdifficult to prevent segregation of active and carrier in concentrationranges above about on preformed granules. When higher concentrations ofactive are desired best results are obtained by premixing powderedactive, diluents, binders and surfactants then granulating so that theactive is distributed throughout the granule and not solely upon itssurface.

Suitable diluents for the preparation of granules by granulation orextrusion include kaolin clays, nonswelling calcium, magnesiummontomorrillonites, and gypsum. Cohesion to a firm granule is usuallyobtained by moistening compacting and drying, with or without somebinding agents. Kaolin clays form firm granules if bound together withgelatinous agents such as methylcellulose, natural clays or swellingbentonite. Calcium, magnesium bentonites require no binder and gypsumcan be made to form firm granules with either the addition of plaster ofparis or certain salts such as ammonium sulfate, potassium sulfate orurea which form double salts with gypsum.

The active content of formed granules can range from 1-90% although 75%active represents about the upper level if controlled disintegration ofthe granule in moist soil is desired. Control of disintegration rate isattained 18 by controlled compaction, e.g., controlled extrusionpressure and by the addition of inert water soluble components such assodium sulfate which can leach away.

Any of the forms of granules described are suitable for use with thecompounds of this invention, the one of choice being dependent upon theintended use.

The following examples illustrate the use of the complexes of thisinvention. Amounts are in parts by weight unless otherwise noted.

EXAMPLE 18 Percent 2-benzimidazolecarbamic acid, methyl ester, 2:1

complex with zinc chloride 70 Alkylnaphthalene sulfonic acid, sodiumsalt 1.5 Oleyl ester or sodium isethionate 2.0 Diatomaceous silica 26.5

The above components are blended and micropulverized, then remilled in afluid energy mill until the active fungicide is substantially all below5 microns.

The resulting wettable formulation is added to water at a rate toprovide 300 parts per million by weight of the active component in thetotal slurry. This dilute preparation is then sprayed on randomlyselected apple trees in a commercial orchard. The spray procedure issuch as to result in the application of liquid at the rate of 3,000liters per hectare. Thus, the active component is applied at the rate of900 grams per hectare. Applications start at the time that the firstspring foilage growth appears and continue at weekly or semimonthlyintervals until one month prior to the normal harvest date for apples.At the time of harvest, trees that had been treated in this manner havehealthy foliage of good color and provide a good yield of high qualityfruit having a good finish. Similar and adjacent trees left unsprayed,on the other hand, have foliage showing disease caused by the fungiVenturia inaequalis (scrab fungus) and Podosphaera leucotricha (powderymildew fungus). The unsprayed trees yield only a few small fruit withdiseased spots caused by the fungus Venturia inaequalis. Thus, the 2benzimidazolecarbamic acid, methyl ester, 2:1 complex with zinc chlorideapplied in the form and by the method described effectively preventsdamage to crop plants caused by certain fungi.

EXAMPLE 19 2-benzimidazolecarbamic acid, isopropylester, 2:1

complex with zinc bromide 70 Sodium salt of sulfonated lignin 2Alkylnaphthalenesulfonic acid, sodium salt 1 Kaolin clay (ASP -Mineralsand Chemicals Co.) 27

Components are blended, micropulverized and air milled as in Example 18.The resulting wettable powder formulation is added to water at a rate toprovide 1,000 parts per million by weight of active ingredient in thefinal solution. This solution is sprayed on alternate rows of grapevines in a vineyard at the rate of 800 liters per hectare. Suchapplications start with the earliest growth in the spring and continueat intervals of 12 to 14 days until harvest time. At harvest time thefoliage on the treated vines is healthy and the yield of marketablefruit is high. The alternate unsprayed grape rows, to the contrary, havefoliage heavily diseased with powdery mildew (caused by the fungus Uncinula necator). Thus, the compound of this invention applied in theproper form and by the method described effectively controls powderymildew.

EXAMPLE 20 Percent 2-benzimidazolecarbamic acid, methyl ester, 1:1

complex with copper(II) monochloride 50 Dioctyl sodium sulfosuccinate 3Sodium N-methyl-N-palmitoyltaurate (44%) 4 Sucrose 43 Components areblended and micropulverized, then double air milled for minimum particlesize.

This wettable powder is added to water in an amount to provide 300 partsper million of the active component in the final spray suspension. Thisliquid preparation is then used to spray randomly selected orange treesin an otherwise untreated grove in California. The application volume isat the rate of 6,000 liters per hectare. The first applica tion is madejust after bloom and it is repeated at monthly intervals until harvesttime. Fruit from the treated trees retains its quality duringtransportation and storage. Much of the fruit from the untreated treesis damaged during storage and transit by green mold caused byPenicilliwm digitaium. Therefore, the compound of this invention appliedin the form and by the method described effectively prevents damage byfungi.

EXAMPLE 21 Percent 2-benzimidazolecarbamic acid, ethyl ester, 1:1complex with zinc monopropionate 70 Dodecyl phenol polyethylene oxidecondensate 4 Synthetic fine silica 26 The liquid surfactant is firstblended with the active component, followed by the diluent. The mix isthen micropulverized and air milled until substantially all of theparticles of active ingredient have a particle size less than 3 microns.

The wettable powder thus prepared is added to water in an amount toprovide 1,000 parts per million of the active ingredient in the totalpreparation. This is used to spray alternate rows in a cherry orchard inWisconsin. Applications at the rate of 1,000 liters per hectare are madestarting with the earliest green tissue in the spring and continuing atintervals of two Weeks until just prior to harvest. The rows of treesthus treated remain healthy and vigorous throughout the growing seasonand produce good quality fruit that keeps well during storage. The treesin the untreated rows show damage to blossoms and fruit caused by thebrown rot fungi (Monilim'a fracticola and M. laxa). Also, the foliage ofthe untreated trees is damaged by the cherry leaf spot organism(Coccomyces hiemalis). The complex of this invention, applied in theproper composition and by the method described protects cherry treesfrom attack by fungi.

EXAMPLE 22 Percent 2 -benzimidazolecarbamic acid, methyl ester, 1:1

complex with copper (II) monoacetate Alkyl naphthalene sulfonic acid,sodium salt 0.5 Attapulgite 10.0 Micaceous talc 79.5

The active attapulgite and surfactant are first blended, micropulverizedand air milled. This fine particled prodnet is then blended with themicaceous talc to form a dust.

The active sugar and surfactant are first blended, micropulverized andair milled. This fine particled product is then blended with themicaceous tale to form a dust.

The above dust is applied with a hand duster to designated plots with alarge cucumber field. Each application is at the rate of 10 kilograms ofthe formulation per hectare. The applications made on the plants startto form runners and are known to be already infected with the powderymildew fungus (Erysz'phe cichoraciarum). At harvest the plants Withinthe treated plots are healthy and yield well. The untreated areasoutside the plots, on the other hand, contain only cucumber plantsheavily diseased with powdery mildew. The compound of this inventionformulated and applied as described provides curative or eradicantcontrol of cucurbit powdery mildew.

20 EXAMPLE 23 Percent 2 benzimidazolecarbamic acid, sec-butyl ester, 1:1

complex with zinc, monoacetate 5 Sodium lauryl sulfate 0.5 Kaolin clay10 Tobacco stem dust 84.5

The first three components are first mixed and finely ground, thenblended with the tobacco dust.

Selected plots in a rice field are dusted with the formulation describedabove employing a hand dust applicator. Application is at the rate of 15kilograms of the formulation per hectare. The first application is madewhen the rice plants are about 10 inches tall and it is repeated atintervals of two weeks until about 14 days prior to harvest. The ricewithin the treated plots remains healthy and yields well. The untreatedareas outside the test plots, however, are heavily infected with therice blast fungus (Piricularia oryzae) and provided only a negligibleyield of low quality grain. The compound of this invention applied bythe method described controls rice blast disease.

EXAMPLE 24 Percent Wettable powder of Example 18 14.3 Expandedvermiculite (0.25-0.60 mm.) 77.7 Polyethylene glycol 400di-triricinoleate 8.0

The wcttable powder and vermiculite are first blended briefly. Theliquid surfactant is then sprayed upon the tumbling solids to preventsegregation in storage and fungicide.

The above granular formulation is applied to the covering soil in theplanting of potato seed-pieces. The granules are dropped over aIO-centimeter band at the rate of 6,000 grams of commodity per 400meters of row as the covering soil is pushed into place. This results inthe applications of approximately 30 parts per million of activeingredient in the soil above the seed pieces. Rows treated in thismanner produce healthy plants which yield Well. Adjacent untreated rows,on the other hand, produce yellowish plants with fungus lesions on thestems near the surface of the soil that yield poorly. The damage in theuntreated rows is caused by the soil borne fungus, Rhizoctonia. Thecompound of this invention applied in the compositions and mannerdescribed protects potato plants from attack by Rhizoctonia present inthe soil.

EXAMPLE 25 Percent Z-benzimidazolecarbamic acid, sec-butyl ester, 2:1

complex with zinc chloride 15 Kaolin clay 82 Methyl cellulose (15 cps.)3

The components are blended, micropulverized and air milled. Theresulting powder is moistened with 1820% water and granulated. Afterdrying the granules are screened to recover the fraction having aparticle size range of 0.25 to 0.60 mm.

The granular formulation described above is applied to a pasture paddockin New Zealand at a rate to provide 2,000 grams of the active componentper hectare. The application is made early in the moist portion of thegrowing period. Sheep grazing in the paddock remain healthy and growwell. Sheep in an adjacent untreated paddock are unhealthy and developsymptoms known as face eczema due to contact with and consumption ofmycelia and spores of the fungus Pithamyces chartomm growing on thegrass plants. The compound of this invention applied in the compositionand by the method described controls Pithomyces chartorum.

21 I claim: 1. A fungicidal composition comprising a fungicidallyeffective amount of a complex of the formula:

R is methyl, ethyl, isopropyl, or sec-butyl; and X is chlorine orbromine, with an adjuvant selected from the group consisting of surfaceactive agents, inert solid diluents, liquid diluents and mixturesthereof.

2. A fungicidal composition comprising a fungicidally effective amountof a complex of the formula:

with an adjuvant selected from the group consisting of surface activeagents, inert solid diluents, liquid diluents and mixtures thereof.

3. A fungicidal composition comprising a fungicidally effective amountof a complex of the formula:

- ZXlClg R is methyl, ethyl, isopropyl or scc-butyl; and

Y is chlorine or bromine, with an adjuvant selected from the groupconsisting of surface active agents, inert solid diluents, liquiddiluents and mixtures thereof.

4. A fungicidal composition comprising a fungicidally effective amountof a complex of the formula:

N t O R C N wherein:

R is methyl, ethyl, isopropyl, or sec-butyl;

M is zinc or copper; and

X is acetate or propionate when M is zinc and is chlorine, bromine,acetate, or propionate when M is copper, with an adjuvant selected fromthe group consisting of surface active agents, inert solid diluents,liquid diluents and mixtures thereof.

5. A method for controlling fungi comprising applying to a locus to beprotected at fungicidally effective amount of a complex of the formula:

R is methyl, ethyl, isopropyl, or sec-butyl; and

X is chlorine or bromine.

6. A method for controlling fungi comprising applying to a locus to beprotected a fungicidally effective amount of a complex of the formula:

7. A method for controlling fungi comprising applying to a locus to beprotected a fungicidally effective amount of a complex of the formula:

R is methyl, ethyl, isopropyl or sec-butyl; and

Y is chlorine or bromine.

8. A method for controlling fungi comprising applying to a locus to beprotected a fungicidally effective amount of a complex of the formula:

ALEX MAZEL, Primary Examiner R. I. GALLAGHER, Assistant Examiner U.S.Cl. X.R. 260-299

